Manufacture of benzanthrone derivatives containing sulphur



Patented Oct. 11, 1927.

WAGTUBIOI Io Drawing. Appneatton flel rein-nary 9, 1820,

We have found that new benzanthrone derivatives containing sulphur can be ob tained by treating.Bz-1-halogen-benzanthrones corresponding to the formula 5 be carried out'in an aqueous suspension.

The new compoundsare sulphinic acids of the benzanthroneseries Their salts are 80 readily transformed into tihgegalts of! the corresponding sulphonic aci y oxi tion in an aqueous solution. By a reducing treatment for examlple with an eous solution of po y-sulphides e corresponding benzanthronyl-mercaptans are obtained, while hlry the action of sodium sulphide at about 0 d to80 tigrade Bz-LBz-Y-bmzanthionyl phides and 8t alooholates.

- phides, while by heating with sul PATE ' usrnm mum CORPORATION OF ssmmr.

a: 1m nnmva'rrvns oorr'ramms summon.

Serial Io. 87,188, and in Germany larch 7, 1925.

higher temperatures isodibenzanthrones are obtained as well as the said mercaptanalfl Isodihenzanthrones are also obtained by fusing the sulphinic acids or their alkyl or acyl derivatives obtainable by alkylation or acylation of the sulphinic acids with alkali metal When heated with inert diluu ents of a, high bo' int, for example parafline oil, the sul 1c acids are transormed into Bz-L z-1'-benzanthronyl-sulhuric acid of 60 degrees Baum at water-ha tern raso ture, Bz-.1.Bz-1'-benzanthronyldisulp ides are obtained which can also be prepared by the action of metals as for example copper or aluminium powder and concentrated sulphuric acid at roomtemperature. 86 ltily reason of the properties above referred to s new benzanthrone derivatives contaim' ing sulphur are valuable intermediates for the production of dyestuffs of the benzan: throne series.

The following examples will further illustrate how the invention may be carried out In tpractice, but the invention isnot. to ese examples. The parts are by welght.

Ewampk 1.

10 parts of finely divided Bz-1chlor-benzanthrone are stirredwith 200 parts of meth- 61.70 parts of per cent a ueous ammonia and 10 parts of dry anhy rous sodium 70 hydrosulphite at about degrees to decenti ade until a test ortion when uted wit water leaves '0 y ve little un'dissolved matter or none at all. e reaction probably takes place according to the following equation:

+m+ 1mm.

ammo.

The alcohol is then distilled oil, the residue dissolved in hot water at the same time introducing air, and the solution, if 11 after filtering off some unaltered chlor-beno zanthrone, is acidulated. The resulting recipitate when dry forms a brownish ve lo Bowder which dissolves water ut readily in dilute 'alkalis wit a ellow color. B. recrystallization from ethy alco- 1101 itfig o tai'ned in crystals melting at about 225 degrees centi'gra e. Whenlonidized in an aqueous sc'alution it isjtransformed into aqueous ammonia" and 10 arts of sodium hydrosulphite to abdut 90 egrees to 95 deeentigrade. r Unaltered brom-benzantum-which'lbfijeirfiii Order to oxidize any mneltered l -hydrosul hite,

30 rated as described in Exam cooled and fecldlilated' with hydroc oric :ecid. The precipitated product is identical "with that described in Exam ile 1.

E'wampl 8.

A mixture of parts'of finely divided Bz-l-chlorbenzenthrone, parts of sodium hydrosulphite and 00 farts of 50 per cent ethyl alcohol is stirred or some hours at 60 degrees to 70 degrees centigrade 'while excludmg air. The reaction laroduct is sepap e 1. E'mriple 4 10V parts of -Bz-1-brom-benzanthrone, 200

parts of ethyl alcohol, 400 parts of water,

parts ofa v per cent caustic sodasolution "and 20 parteef sodium formaldehyde sul hin Example 3;

Whetweclaim is: i

1. The process of manufacturing newhenzanthrone derivatives which consists in treating Bz-l-halogen-benzanthrones with a oxylate aretrea'tedin the manner d hydrosulphite at solow a temperature that 7 nofurthr conversion of the resulting :snl-

fphinic acids takes place.

i 2. As new articles of manufacture, BZI:

benzanthrone sulphinie acids.

3. As new article of manuf acture, Bz -1- benzanthrone sulphinic acid having the for mula In testimony whereof our hands. HEINRICH. NER-ESHEIMER.

HANS ELflZl ER. v

we have hereunto set w der which dissolves eat er Ext readily in dilute alkalis wi a ellow color. B recrystallization from ethy c. When oxidized in s 225 degrees centigra it is transformed into an aqueous solution benzanthrone-s'ulphouic acid Ewample'fl. f 10 10 parts of fin'ely divided Bz l brom-henzanthrone are heated V for some hours with 200 parts of water, 70 parts of 20 percent aqueous ammonia and 10 hydrosulphite to about "90 centigrade. Unaltered brom-benzan- I ne is then filtered oil from the hotmiirtare, which is'then treated-with 'airiin order to oxidize any unalteretl hydmsul hi'te, cooled and -jacidu'lated' with hydr oric acid. The precipitated product is identical 'Wifll that described in Example 1. E'ammple 8.

A mixture of 10 partsof finely divided as Bz-l-chlorbenzanthrone, parts of sodium hydrosulphite and 400 arts of 50 per cent ethyl alcohol is stirred or some hours at 60 degrees to 70 degrees centigrade 'while excludmg air. The reaction product is separated as described in Example 1.

Emwiple 4.

10 parts of 'Bz-l-brom-benzanthrone, parts of ethyl alcohol, 400

agrees to 95 de- 200 parts of water,

alcohol itis o .tained in cgystals melting at about in Example 3.

.i'phinic acids takes place. 7 2;. As new articles of manufacture, Bz-J; I

em of sodium benzanthrone sulphin ic acids.

ongest .psrts ofa 85 per cent caustic soda solution and 20 partso'f sodium formaldehyde sul h- 35 are treated in the manner descri d oxylate Whatwe .claim is: V

I 1. The process of manufacturing newbenzanthrone derivatives 'which treating Bz-l-halogen-benzanthrones with a hydrosulphite at so low a temperature that no further conversion of the resulting sul- 3. As new article of manufacture, Bz -1- benzanthrone sulphinic acid having the formule.

In testimony whereof vve have hereunto set our hands. V HEINRICH .NERESHEIMER. HANS MM ER. v

a hie-mo, 1.644.851.

mansion awe ome, 11,192; m

:' can: ET AL.

I. i that. tlie sheveaumbered-pstent-wss erroneously issued to Aktiengesellschsft, of Frsnklort-on-the-Msin, I Generational Germany"; irheress ssitl Intent have been issued to v Grsssel'li"Dyestnfiporporstien, of New York; N. Y.,, s Corporation of ti Delaware", ss itl Corporation bei sjs'sslgsee lnesne sssisnnentsot theen tI'fei 7 interest in said invention, sssllewnfllyrthe reeordsof assignments If! 0 es,

and, that the ssidlteu'ers Patent the 13 be read with this'eorrsction therein that: as! conform to the 'qflffllt ease in the'l'stesttlf fiee.

a A lie-3. mm. Actim' Commissioner ofjPstents.-

consists in 40 CERTIFICATE OF comcnon.

mm No. 1,644,851. GrantedOctober 11, 1927, m

HEINRICH NERESHEIMER ET AL.

it is hereby certified that the above numbered patent was erroneously issued to "I. G. Farbenindustrie Aktiengeselischaft, of Frankfort-on-the-Main, Germany, a Uorporation of Germany"; whereas said patent should have been issued to "Grasselli Dyestnff Corporation, of New York, N. Y., [Corporation of Delaware", said Cornoration beingassignee by mesnc assignments of the entire interest in said invention, as shown by the records of assignments in this office; .and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 8th day of November, D. 1927.

" i hi. J. Moore,

Seal. Acting Commissioner of Patents; 

